CN114456336B - Preparation method and application of ultraviolet degradable polymer material - Google Patents
Preparation method and application of ultraviolet degradable polymer material Download PDFInfo
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- CN114456336B CN114456336B CN202210288612.XA CN202210288612A CN114456336B CN 114456336 B CN114456336 B CN 114456336B CN 202210288612 A CN202210288612 A CN 202210288612A CN 114456336 B CN114456336 B CN 114456336B
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- 239000002861 polymer material Substances 0.000 title claims abstract description 23
- 229920006237 degradable polymer Polymers 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 24
- 230000001052 transient effect Effects 0.000 claims abstract description 24
- 238000006731 degradation reaction Methods 0.000 claims abstract description 21
- 230000015556 catabolic process Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 claims description 8
- 229910015900 BF3 Inorganic materials 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- 238000001226 reprecipitation Methods 0.000 claims description 4
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000005297 material degradation process Methods 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 79
- 230000015572 biosynthetic process Effects 0.000 description 18
- 239000010409 thin film Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- QRHHZFRCJDAUNA-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical group C1=CC(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 QRHHZFRCJDAUNA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229940054441 o-phthalaldehyde Drugs 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G6/00—Condensation polymers of aldehydes or ketones only
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/02—Condensation polymers of aldehydes or ketones only
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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Abstract
The invention discloses a preparation method of an ultraviolet degradable polymer material, which comprises the steps of carrying out polymerization reaction under the action of a catalyst to obtain a metastable polymer polyphthalaldehyde; compared with the normal temperature and normal pressure process, the film prepared by the method has uniform distribution, smooth surface and no bubble, can meet the quality requirement of electronic devices on materials, is very convenient for the subsequent preparation of the electronic devices, can be controllably degraded in the ultraviolet light wave band with the wavelength of 310-390 nm, and can realize the controllable degradation time of the transient film material by changing the material degradation time by changing the proportion of components in the film preparation process.
Description
Technical Field
The invention relates to the technical field of organic materials, in particular to a preparation method and application of an ultraviolet light degradable polymer material.
Background
The rapid development of electronic devices and equipment provides many convenience for the life of people, and the electronic devices with excellent performance and strong durability are always targets of researchers in the past decades, so that substrate materials and electronic materials adopted by the electronic devices and equipment are stable and are not easy to degrade; therefore, most of the discarded electronic devices are toxic and cause a certain pollution to the environment. With the expansion of the usage amount of electronic devices, electronic equipment which is damaged or eliminated from any place and any time is abandoned, and the abandoned electronic devices cannot be naturally degraded under natural conditions, so that serious environmental pollution is brought, and one of the important problems threatening the life of human society has been developed.
The transient electron is an important method for solving the problem, is also a hot spot field of current research, and is stable in high performance in a working chamber, and degradation of an electronic device can be realized in a short time when the transient electron is needed. At present, the method plays an important role in the aspects of information safety, biological medical treatment, environmental sensors and the like. Compared with the traditional electronic device, the transient electronic device can realize the disappearance of physical form and device function under the regulation and control of external stimulus or related instructions. However, the transient materials of the prior art are harsh in controllable conditions and unstable in material properties.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a preparation method of an ultraviolet light degradable polymer material, so as to solve the problems that the degradation time is difficult to control, the prepared film material is poor in form and the application of the film material is influenced in the prior art.
In order to solve the technical problems, the invention provides a preparation method of an ultraviolet light degradable polymer material, which comprises the following steps:
(1) Adding phthalic dicarboxaldehyde into a reactor, enabling the reactor to reach a vacuum state, filling nitrogen into the reactor, and then adding anhydrous dichloromethane into the reactor; wherein, the concentration of the phthalic dicarboxaldehyde in the anhydrous dichloromethane is 0.01 g/mL-0.3 g/mL;
(2) Stirring the solution in the reactor, cooling the solution in the reactor to below-78 ℃, and adding boron trifluoride ether into the reactor; wherein the content of boron trifluoride ether in the solution in the reactor is 0.005 g/mL-0.02 g/mL;
(3) Adding pyridine after stirring the solution in the reactor for 1-2 h, continuously stirring the solution in the reactor for 1-2 h, then placing the reactor in a room temperature environment, and pouring the mixture in the reactor into methanol to form white floccule precipitate; wherein the concentration of pyridine in the solution in the reactor is 0.02 g/mL-0.08 g/mL.
(4) Dissolving the white floccule precipitate obtained in the step (3) in anhydrous dichloromethane to obtain a mixed solution, pouring the mixed solution into methanol for reprecipitation, and further purifying to obtain white blocky fiber; and drying the fiber to volatilize methanol in the fiber to obtain an ultraviolet light degradable polymer material, namely the polyphthalaldehyde cPPA.
Furthermore, the invention also provides an application of the ultraviolet light degradable polymer material, namely, the polymer material prepared by the preparation method is utilized to prepare the polyphthalaldehyde film. The method specifically comprises the following steps:
adding a polymer material of polyphthalaldehyde cPPA, a photoacid generator MBTT, a curing agent DGD and an organic solvent dioxane into a light-proof sample bottle, uniformly stirring to obtain a reaction solution, transferring the reaction solution into a container, and carrying out negative pressure constant temperature treatment on the reaction solution to obtain a smooth and complete light radiation transient film;
in the reaction solution, the concentration of the polyphthalaldehyde is 0.05 g/mL-0.3 g/mL; the concentration of the photoacid generator MBTT is 3 mg/mL-10 mg/mL; the concentration of the curing agent diethylene glycol dibenzoate is 0.1 mg/mL-0.3 mg/mL; the balance of organic solvent dioxane.
The conditions of the negative pressure constant temperature treatment are as follows: the temperature is 20-100 ℃, the negative pressure is minus 0.4MPa to minus 1.0MPa, and the mixture is kept stand for 4-10 h.
Compared with the prior art, the invention has the following beneficial effects:
1. the method for preparing the ultraviolet degradable polymer material carries out polymerization reaction under the action of a catalyst, and is matched with a repeated precipitation method for purification, and the precipitation is dissolved and purified for a plurality of times, so that the purity of the product is obviously improved, and the metastable annular polymer phthalic dicarboxaldehyde is finally obtained.
2. The transient film is prepared by using the polymer polyphthalaldehyde obtained by the method of negative pressure and constant temperature, the obtained film is uniformly distributed, has smooth surface and no bubble, can meet the quality requirement of an electronic device on materials, and is very convenient for the subsequent preparation of the electronic device. And the degradation time of the material can be changed by changing the proportion of components in the film preparation process, so that the degradation time of the transient film material can be controlled. The obtained transient film is controllably degraded in the ultraviolet light wave band with the wavelength of 310-390 nm.
Drawings
FIG. 1 is a diagram of a thin film material (physical) prepared in example 6 of the present invention.
Fig. 2 is a process diagram of degradation (physical) of the thin film material prepared in example 6 of the present invention under an ultraviolet lamp.
FIG. 3 is a line graph showing the fastest degradation time for the degradable film of example 6 of the present invention at different photoacid generator concentrations.
FIG. 4 is an H NMR spectrum of a polymer degradable film.
FIG. 5 is an effect diagram of different film preparation modes: drying (a) at normal temperature (b) heating and drying (c) at negative pressure and constant temperature.
Fig. 6 is a graph of film formation at various negative pressures: (a) film formation under-0.4 MPa, (b) film formation under-0.6 MPa, (c) film formation under-0.8 MPa, and (d) film formation under-1.0 MPa.
Film formation at different temperatures in fig. 7: (a) film formation at 20 ℃ (b) film formation at 30 ℃ (c) film formation at 40 ℃ (d) film formation at 50 ℃.
Fig. 8 is a real-time content of cPPA material in a transient film.
Detailed Description
The invention will be described in further detail with reference to the drawings and examples.
1. Preparation method of ultraviolet degradable polymer material
(1) Adding phthalic dicarboxaldehyde into a reactor, enabling the reactor to reach a vacuum state, filling nitrogen into the reactor, and then adding anhydrous dichloromethane into the reactor; wherein, the concentration of the phthalic dicarboxaldehyde in the anhydrous dichloromethane is 0.01 g/mL-0.3 g/mL;
(2) Stirring the solution in the reactor, cooling the solution in the reactor to below-78 ℃, and adding boron trifluoride ether into the reactor; wherein the content of boron trifluoride ether in the solution in the reactor is 0.005 g/mL-0.02 g/mL;
(3) Adding pyridine after stirring the solution in the reactor for 1-2 h, continuously stirring the solution in the reactor for 1-2 h, then placing the reactor in a room temperature environment, and pouring the mixture in the reactor into methanol to form white floccule precipitate; wherein the concentration of pyridine in the solution in the reactor is 0.02 g/mL-0.08 g/mL.
(4) Dissolving the white floccule precipitate obtained in the step (3) in anhydrous dichloromethane to obtain a mixed solution, pouring the mixed solution into methanol for reprecipitation, and further purifying to obtain white blocky fiber; and drying the fiber to volatilize methanol in the fiber to obtain an ultraviolet light degradable polymer material, namely the polyphthalaldehyde cPPA.
In the step (4), after reprecipitating the mixed solution in methanol, taking out the white precipitate, adding 1-2 mL of anhydrous dichloromethane into the white precipitate to enable the o-PA monomer which is not completely polymerized and other impurities to be completely dissolved, pouring 10mL of methanol into the solution, taking out an insoluble block, adding 2mL of dichloromethane into the insoluble block to enable the insoluble block to be completely dissolved, adding 10mL of methanol, and repeatedly precipitating to obtain pure cPPA polymer material, wherein the purity of the polymer obtained by calculation can reach more than 97%.
Referring to Table 1, the qualified ultraviolet light degradable polymer material polyphthalaldehyde cPPA can be prepared according to the following proportion. Wherein, o-phthalaldehyde/boron trifluoride ether/pyridine is a substance which participates in the reaction; the balance of anhydrous dichloromethane is used as solvent. In addition, since most of the by-products are soluble in formaldehyde and the polymer is insoluble in formaldehyde, most of the by-products in the reaction product can be removed by formaldehyde, thereby obtaining a cPPA polymer material of higher purity.
TABLE 1
2. Application of ultraviolet degradable polymer material
Namely, the polymer material polyphthalaldehyde cPPA obtained by the preparation method is used for preparing a polyphthalaldehyde film, and specifically comprises the following steps:
adding a polymer material of polyphthalaldehyde cPPA, a photoacid generator MBTT, a curing agent DGD and an organic solvent dioxane into a light-proof sample bottle, uniformly stirring to obtain a reaction solution, transferring the reaction solution into a container, and carrying out negative pressure constant temperature treatment on the reaction solution to obtain a smooth and complete light radiation transient film.
Wherein the photoacid generator MBTT is 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -S-triazine; the curing agent DGD is diethylene glycol dibenzoate; the solvent dioxane is 1, 4-dioxane, and the molecular formula is C 4 H 8 O 2 。
In the reaction solution, the concentration of the polyphthalaldehyde is 0.05 g/mL-0.1 g/mL; the concentration of the photoacid generator MBTT is 3 mg/mL-8 mg/mL; the concentration of the curing agent DGD is 0.01 mg/mL-0.3 mg/mL.
Wherein, the conditions of the negative pressure constant temperature treatment are as follows: the temperature is 20-100 ℃, the negative pressure is minus 0.4MPa to minus 1.0MPa, and the mixture is kept stand for 4-10 h. Within this range, the light radiation transient film with a uniform and smooth surface can be obtained by selecting the determined preparation parameters.
Taking example 1 as an example, the content of MBTT was changed to prepare polyphthalaldehyde examples 10-13, and film material examples 6-9 were prepared respectively using examples 10-13 as raw materials.
Referring to table 2, the degradation time of the transient thin film can be changed by changing the content of the photoacid generator MBTT in the light-radiating transient solution.
TABLE 2
As shown in FIG. 1, the film material (physical object) obtained in example 6 was obtained.
FIG. 2 is a (physical) process diagram showing degradation of the thin film material prepared in example 6 under an ultraviolet lamp. The degradation process is characterized by utilizing nuclear magnetic resonance hydrogen spectrum, and as shown in fig. 4, the degradation degree of the transient thin film can be obtained. As can be seen from fig. 2, in the ultraviolet band at a wavelength of 310 to 390nm, significant degradation takes only 35 minutes.
FIG. 3 is a line graph of the fastest degradation time of a degradable film at different photoacid generator concentrations. From this, it can be seen that the degradation time of the film gradually shortens with increasing MBTT content; therefore, the degradation time of the degradable film can be regulated and controlled by regulating the MBTT content.
TABLE 3 Table 3
| Examples | Temperature (. Degree. C.) | Negative pressure (MPa) | Standing time (h) | Film morphology |
| 10 | 30℃ | -0.4MPa | 15h | The surface of the film is uniformly dried |
| 11 | 30℃ | -0.6MPa | 8h | The surface of the film is uniformly dried |
| 12 | 30℃ | -0.8MPa | 6h | The surface of the film is partially dry and cracked |
| 13 | 40℃ | -0.4MPa | 12h | A small amount of oil-filled liquid appears on the surface of the film |
| Comparative example 1 | 30℃ | 0MPa | 18h | The liquid is gathered into a group, and can not form a film package |
| Comparative example 2 | 30℃ | -1MPa | 6h | The film becomes brittle and does not haveFlexible features |
| Comparative example 3 | 30℃ | -0.6MPa | 4h | Without forming a film, the surface also has obvious liquid |
It can be seen from table 3 that the selection of the negative pressure constant temperature treatment conditions has a significant effect on the morphology of the resulting light-radiating transient film. The film preparation effect under different conditions is shown in figure 5.
FIG. 5 is an effect diagram of different film preparation modes: (a) drying at normal temperature; (b) heating and drying; (c) negative pressure constant temperature.
As can be seen from fig. 5, a complete thin film cannot be formed under the condition of normal temperature drying; the film forming is uneven under the condition of heating and drying, the thickness of the film is inconsistent, and the film effect obtained by utilizing negative pressure constant temperature is best.
Fig. 6 is a graph of film formation at various negative pressures: (a) forming a film at-0.4 MPa; (b) forming a film at-0.6 MPa; (c) film formation under-0.8 MPa (d) film formation under-1.0 MPa.
As can be seen from FIG. 6, the film prepared under the pressure of-0.4 MPa has a part of fluidity liquid, and the liquid is gathered together, only forms a film shape on the surface of the liquid, and cannot be completely dried to form a film; the film prepared under the pressure of-0.6 MPa is uniformly distributed and has a flat surface, and is easy to be stripped from the substrate; the film prepared under the pressure of-0.8 MPa is formed, but the surface of the film is unevenly distributed and has obvious lines, so that the film cannot meet the film preparation requirement; the surface of the film manufactured under the pressure of-1.0 MPa has a plurality of obvious cracks and the surface of the film is rugged, and the film cannot meet the film manufacturing requirement.
Fig. 7 shows film formation at different temperatures: (a) film formation at 20 ℃; (b) film formation at 30 ℃; (c) film formation at 40 ℃; (d) film formation at 50 ℃.
As can be seen from fig. 7, the surface of the film formed at 20 ℃ (fig. a) under negative pressure had significant liquid, indicating that the film did not dry out at this temperature; the surface of the film is free of liquid at 30 ℃ (picture b) and is uniformly distributed; at 40 ℃ (panel c) the film texture became viscous and a small amount of yellow oil droplets appeared on the surface.
3. Verification experiment
Referring to FIG. 2, the thin film materials prepared in examples 6 to 10 were irradiated under the ultraviolet light band having the wavelength of 310 to 390nm, while observing the state of the thin film materials. The degradation process is characterized by utilizing nuclear magnetic resonance hydrogen spectrum, and as shown in fig. 4, the degradation effect of the transient thin film can be obtained by knowing the degradation degree of the transient thin film.
Fig. 8 is a real-time content of cPPA material in a transient film.
The transient film was irradiated under an ultraviolet lamp, and the cPPA material content in the film was characterized every five minutes, and it was seen that the cPPA content was finally reduced from 89% to 19.8%.
In conclusion, the transient film is prepared by using the polymer polyphthalaldehyde obtained by the method of negative pressure and constant temperature, the obtained film is uniformly distributed, has smooth surface and no bubble, can meet the quality requirement of an electronic device on materials, and is very convenient for the subsequent preparation of the electronic device. And the degradation time of the material can be changed by changing the proportion of components in the film preparation process, so that the degradation time of the transient film material can be controlled. The obtained transient film is controllably degraded in the ultraviolet light wave band with the wavelength of 310-390 nm.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the technical solution, and those skilled in the art should understand that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the present invention, and all such modifications and equivalents are included in the scope of the claims.
Claims (2)
1. The application of the ultraviolet light degradable polymer material is characterized in that the polyphthalaldehyde film is prepared by utilizing polyphthalaldehyde; the method for preparing the polyphthalaldehyde film comprises the following steps:
adding a polymer material of polyphthalaldehyde cPPA, a photoacid generator MBTT, a curing agent DGD and an organic solvent dioxane into a light-proof sample bottle, uniformly stirring to obtain a reaction solution, transferring the reaction solution into a container, and carrying out negative pressure constant temperature treatment on the reaction solution to obtain a smooth and complete light radiation transient film;
in the reaction solution, the concentration of the polyphthalaldehyde is 0.05 g/mL-0.3 g/mL; the concentration of the photoacid generator MBTT is 0.5mg/mL, 1.0mg/mL, 1.25mg/mL or 2.0mg/mL; the concentration of the curing agent diethylene glycol dibenzoate is 0.1 mg/mL-0.3 mg/mL;
under the ultraviolet light wave band with the wavelength of 310-390 nm, the degradation time of the degradable film can be regulated and controlled by adjusting the MBTT content;
the conditions of the negative pressure constant temperature treatment are as follows: the temperature is 30 ℃, the negative pressure is minus 0.6MPa, and the mixture is stood for 4 to 10 hours;
the polyphthalaldehyde is prepared by the following method:
(1) Adding phthalic dicarboxaldehyde into a reactor, enabling the reactor to reach a vacuum state, filling nitrogen into the reactor, and then adding anhydrous dichloromethane into the reactor; wherein the concentration of the phthalic dicarboxaldehyde in the anhydrous dichloromethane is 0.01 g/mL-0.3 g/mL;
(2) Stirring the solution in the reactor, cooling the solution in the reactor to below-78 ℃, and adding boron trifluoride ether into the reactor; wherein the content of boron trifluoride ether in the solution in the reactor is 0.005-g/mL-0.02-g/mL;
(3) Adding pyridine after stirring the solution in the reactor for 1-2 hours, continuously stirring the solution in the reactor for 1-2 hours, then placing the reactor in a room temperature environment, and pouring the mixture in the reactor into methanol to form white floccule precipitate; wherein the concentration of pyridine in the solution in the reactor is 0.02 g/mL-0.08 g/mL;
(4) Dissolving the white floccule precipitate obtained in the step (3) in anhydrous dichloromethane to obtain a mixed solution, pouring the mixed solution into methanol for reprecipitation, and further purifying to obtain white blocky fiber; and drying the fiber to volatilize methanol in the fiber to obtain an ultraviolet light degradable polymer material, namely the polyphthalaldehyde cPPA.
2. The use of an ultraviolet light degradable polymeric material according to claim 1, wherein in step (4), after reprecipitation of the mixed solution in methanol, the white precipitate is taken out, anhydrous methylene chloride is added to the white precipitate, so that the o-PA monomer which is not completely polymerized and other impurities are completely dissolved, and then methanol is poured into the solution, and insoluble lumps are taken out; and adding dichloromethane into the insoluble block to completely dissolve the insoluble block, and repeatedly precipitating with methanol to collect the ultraviolet degradable polymer material polyphthalaldehyde cPPA.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002296402A (en) * | 2000-08-29 | 2002-10-09 | Jsr Corp | Radiation-sensitive variable refractive index composition and method for varying refractive index |
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